JP5079221B2 - Masterbatch composition, polyolefin resin composition containing the same, and molded article thereof - Google Patents

Description

  The present invention relates to a masterbatch composition, a polyolefin-based resin composition containing the masterbatch composition, and a polyolefin molded body obtained using the resin composition. More specifically, a master batch composition containing a plastic additive, an olefin polymer having specific physical properties and a polyolefin resin for a carrier in a specific ratio, a polyolefin resin composition containing the master batch composition, and the The present invention relates to a polyolefin molded body using a resin composition, particularly an injection molded body used for automobile interior and exterior materials.

Polypropylene resins are excellent in rigidity and impact strength and are widely used. In particular, molded products obtained by molding a composition made of polypropylene resins into automobile materials by injection molding or the like are used. It has become to. In addition to mechanical properties such as rigidity and impact resistance strength, these molded products have been required to have an excellent appearance such as a sense of unity with the automobile body, luxury, and high design. Improvements in operability are required for cost reduction.
On the other hand, a pre-manufactured masterbatch composition containing relatively high concentrations of pigments used for coloring and additives such as softeners, fillers, and mold release agents is used as a polypropylene resin for molding materials. By blending and molding, improvements in physical properties and operability of the obtained molded body are achieved.
In this technique, there is a technique in which the same polypropylene resin as the molding material polypropylene resin is used as the carrier resin for the masterbatch composition. If this is the same polypropylene resin, it is considered that the master batch composition is highly dispersed in the polypropylene resin and the appearance is improved due to good compatibility. Since the resin has a high molecular weight, it has a high melt viscosity, and when the pigment content is about 30% by mass or more, there arises a problem that kneadability and moldability become difficult. Further, since the crystallinity is high and the crystallization speed is high, the phase separation between the additive and the polypropylene resin as the carrier proceeds. Therefore, the additive amount cannot be increased, and the operability is not improved. In addition, additives having a lower melting point than polypropylene resins such as lubricants, antistatic agents, heat stabilizers, UV absorbers, etc., have a low melt viscosity and are used in an extruder for producing a resin composition. There are drawbacks such as insufficient kneading.

  Attempts have also been made to use polypropylene waxes with reduced molecular weights as masterbatch carriers. This solves the above-mentioned melt viscosity problem, but since the crystallinity is high, the melting point is high, and when producing a masterbatch composition, a foaming agent, a modifier, a crosslinking agent, etc. are melt-kneaded at a high temperature, For this reason, these additives have a drawback that they undergo chemical changes and cause foaming, crosslinking, decomposition or grafting reactions. In particular, additives such as flame retardants, foaming agents, deodorants, antibacterial and antifungal agents are exposed to high temperatures when melt processing polyolefin resins, and these chemicals or additives evaporate and sublimate, greatly increasing the active ingredients. However, the problem that the additives cannot be filled at a high rate because the crystallization speed is high is not solved.

A method of using atactic polypropylene as a carrier resin for a masterbatch having a low molecular weight and a low melting point has been proposed. In this case, it is possible to disperse a higher concentration of pigment in the masterbatch composition and reduce the color processing cost, but since atactic polypropylene is a by-product when producing polypropylene, it is inexpensive. On the other hand, because there are many catalyst and solvent residues, it can cause odor and color when preparing the masterbatch composition, and the color of the molded product obtained using the masterbatch composition However, there is a problem that the color of the molded body becomes difficult due to a slight change. Further, since it is a by-product, there is a problem that the physical property value, for example, the melt viscosity varies greatly, the fluidity becomes unstable during kneading, and the operability is poor.
A method for producing an antistatic masterbatch using the atactic polypropylene as a carrier (for example, see Patent Document 1), a method for producing a coloring or modifying masterbatch (for example, see Patent Documents 2 and 3), etc. are proposed. Has been. Since these methods use atactic polypropylene, which is a by-product of polypropylene production, as a raw material, the above-described drawbacks are included. In addition, it has also been proposed to use an amorphous polyolefin random copolymer produced not for by-products but as a carrier resin for a masterbatch (see, for example, Patent Documents 4 and 5). However, since the copolymer is a copolymer obtained using a heterogeneous catalyst, the molecular weight distribution and composition distribution are wide. That is, it contains a high molecular weight component having a high melting point and a low molecular weight component having an amorphous low melting point. This low molecular weight component becomes a sticky component and has the problem that it leads to adhesion between master batch pellets and stickiness of the resulting molded article. In the above proposal, it is described that it is preferable to use an anti-tacking agent when there is tackiness. When the molded product becomes sticky, the mold release property of the molded product during injection molding is lowered, which leads to a decrease in operability and a deterioration in appearance.

  Furthermore, a colored resin composition using a polypropylene wax obtained by using a metallocene catalyst as a dispersant has been proposed (see, for example, Patent Documents 6 and 7). However, since the melting point is at least 90 ° C., in order to prevent deterioration and reaction of the additive used, a carrier for a master batch having a lower melting point is desired. Further, since the wax used here has a melting point lowered by copolymerization with ethylene or the like, it is necessary to make a copolymer having a high ethylene content in order to lower the melting point. There is a problem that the compatibility with the resin is reduced.

JP-A-62-62836 JP 52-126449 A JP-A-53-67750 Japanese Patent Laid-Open No. 1-261440 JP-A-7-82424 JP 2003-183447 A JP 2003-525340 A

  A masterbatch composition useful for the production of polyolefin resin, particularly polypropylene resin injection moldings, and more specifically, improves the dispersibility of additives in polyolefin moldings, particularly polypropylene moldings, and masterbatch compositions. Highly filled with various additives, master batch composition having good operability without stickiness, suppressing thermal deterioration and reaction of the additive during production of the master batch composition, and polyolefin containing the composition An object of the present invention is to provide a resin-based resin composition and a polyolefin molded body using the resin composition.

  The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, a masterbatch composition containing a specific ratio of an additive for plastics, an olefin polymer having a specific physical property value, and a polyolefin resin for a carrier becomes a masterbatch composition having no stickiness and good operability. Therefore, when a polyolefin-based resin composition containing the masterbatch composition is used, a molded product having good mold releasability from the mold during injection molding, good operability, and excellent appearance can be obtained. Based on this finding, the present invention has been completed.

That is, this invention is comprised from the following.
(1) 35 to 85 % by mass of additive for plastic, 5 to 25 % by mass of olefin polymer satisfying the following (i) to (iii), and 10 to 60 % by mass of polyolefin resin for carrier Masterbatch composition,
(I) Mesopentad fraction [mmmm] is 20 to 80 mol%,
(ii) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. A melting point (Tm-D) defined as the observed peak top of 0-100 ° C.,
(Iii) When the weight average molecular weight (Mw) in the measurement by gel permeation chromatography (GPC) method is in the range of 10,000 to 80,000 and the number average molecular weight in the measurement by GPC method is Mn The Mw / Mn ratio Mw / Mn is 4 or less.
(2) The master batch composition according to (1), wherein the olefin polymer is a propylene polymer that further satisfies the following (iv):
(Iv) Stereoregularity index [mm] is 50 to 90 mol%.
(3) A polyolefin-based resin composition obtained by blending the masterbatch composition according to (1) or (2) above with a polyolefin-based resin,
(4) 0.1 to 10 parts by mass of the masterbatch composition described in (1) or (2) above is blended with 100 parts by mass of a polyolefin resin. Production method of polyolefin resin composition,
(5) The polyolefin resin composition according to (3 ), wherein the polyolefin resin is a polypropylene resin,
(6) The method for producing a polyolefin resin composition according to (4), wherein the polyolefin resin is a polypropylene resin ,
(7) a method of manufacturing the (3) or (5) Po Li olefin moldings by injection molding a polyolefin resin composition according to,
( 8 ) An injection molded article for automobiles formed by injection molding using the polyolefin resin composition according to (3) or (5) ,
It is.

  According to the present invention, a masterbatch composition useful for producing an injection molded product of a polyolefin-based resin, particularly a polypropylene-based resin, more specifically, improving the dispersibility of additives in a polyolefin molded product, particularly a polypropylene molded product. In addition, the masterbatch composition can be highly filled with various additives, the masterbatch composition having good operability without stickiness and suppressing thermal deterioration and reaction of the additive during the production of the masterbatch composition, A polyolefin resin composition containing the composition and a polyolefin molded body using the resin composition can be provided.

  The masterbatch composition of the present invention is a masterbatch composition containing a specific amount of an additive for plastics, an olefin polymer having a specific physical property value, and a polyolefin resin for a carrier.

A. Additives for plastics Additives for plastics used in the present invention include pigments, crosslinking agents, decomposition agents, softeners, mold release agents, antibacterial / antifungal / insect repellents, flame retardants generally used in plastics, Examples thereof include foaming agents, deodorizing agents, lubricants, antistatic agents, heat stabilizers, ultraviolet absorbers, metal powders, and ceramic powders .
Examples of the metal powder include metal powders such as iron, copper, aluminum, titanium, and stainless steel.
Examples of the ceramic powder include oxide ceramic powders such as zirconia and alumina.

  As the pigment, one or more of an organic pigment and an inorganic pigment can be used, and examples of the organic pigment include azo pigments such as azo lake, hansa, benzimidazolone, diarylide, pyrazolone, yellow, and red; Examples thereof include phthalocyanine-based, quinacridone-based, perylene-based, perinone-based, dioxazine-based, anthraquinone-based, isoindolinone-based polycyclic pigments, and aniline black. Examples of the inorganic pigments include inorganic pigments such as titanium oxide, titanium yellow, iron oxide, ultramarine blue, cobalt blue, chromium oxide green, yellow lead, cadmium yellow, and cadmium red, and carbon black.

As a crosslinking agent and a decomposing agent, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-dibutylperoxyhexane, 1,3-bis (t-butylperoxyisobrovir) benzene, 2,2 ′ -Organic peroxides such as azobisisobutyronitrile can be mentioned.
Examples of the antibacterial / antifungal / insect repellent include compounds such as thiosulfamide, thiophthalimide, biszenoxyarsine, thiabetasol, and aminobenzimidazole, and derivatives thereof.
Examples of the flame retardant include compounds such as antimony oxide, organic phosphate ester, chlorendic acid, tetrabromophthalic anhydride, and a polyol containing a phosphorus atom or a halogen atom.
Examples of the blowing agent include compounds such as sodium hydrogen carbonate, dinitrosotetramine, azodicarbonamide, azobisisobutyronitrile, sulfonyl hydrazide, sulfonyl semicarbazide, and derivatives thereof.

B. Olefin Polymer The olefin polymer is an olefin homopolymer or a copolymer of two or more olefins. Here, specific examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 3-methyl- An α-olefin having about 2 to 20 carbon atoms, such as 1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; Cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa In addition to cyclic olefins having 3 to 20 carbon atoms such as hydronaphthalene, styrene, vinylcyclohexane, diene, and the like can be given.
Among them, a polymer having an olefin having 2 to 6 carbon atoms as a main constituent unit is preferable, and a propylene-based polymer having a propylene unit as a main constituent unit and 1-butene having a 1-butene unit as a main constituent unit. A polymer is preferred.

The following are preferable propylene polymers.
A propylene homopolymer having a propylene content of 50 to 100 mol%, ethylene or an α-olefin having 4 to 20 carbon atoms, or propylene and ethylene or an α-olefin having 4 to 20 carbon atoms and Copolymer, preferably propylene 70-100 mol%, ethylene or a C4-20 α-olefin 30-30 mol% propylene homopolymer or propylene and ethylene or a C4-20 α-olefin Copolymer, more preferably propylene 90-100 mol%, ethylene or a C4-20 α-olefin propylene homopolymer or propylene and ethylene or a C4-20 α-olefin And particularly preferably a propylene homopolymer.

The 1-butene polymer is preferably the following.
1-butene homopolymer or 1-butene containing 50 to 100 mol% of 1-butene, 50 to 0 mol% of α-olefin having 2 to 20 carbon atoms (excluding those having 4 carbon atoms) And an α-olefin copolymer having 2 to 20 carbon atoms (excluding those having 4 carbon atoms), preferably 70 to 100 mol% of 1-butene and 30 to 0 mol% of an α-olefin having 2 to 20 carbon atoms. 1-butene homopolymer or a copolymer of 1-butene and an α-olefin having 4 to 20 carbon atoms (excluding those having 4 carbon atoms), more preferably 90 to 100 mol% of 1-butene, 1-butene homopolymer of 10 to 0 mol% of α-olefin having 2 to 20 carbon atoms (excluding those having 4 carbon atoms) or 1-butene and 2 to 20 carbon atoms (however, having 4 carbon atoms) Copolymer) with α-olefin, particularly preferred Ku is a 1-butene homopolymer.

The olefin polymer used in the present invention must satisfy the following physical property requirements.
(I) Mesopentad fraction [mmmm] is 20 to 80 mol%, preferably 30 to 70 mol%, more preferably 30 to 55 mol%, particularly preferably 35 to 50 mol%.
In addition, in the 1-butene polymer, a preferable mesopentad fraction [mmmm] is 40 to 85 mol%, more preferably 60 to 80 mol%, particularly preferably 65 to 80 mol%.
Here, the mesopentad fraction [mmmm] is obtained in accordance with the method proposed in Macromolecules, 6925 (1973) reported by A. Zambelli et al. That is, the signals of methylene group and methine group are measured using ¹³ C nuclear magnetic resonance spectroscopy, and mesopentad fractions [mmmm], [mmrr] and [rmmr] are obtained. For 1-butene polymers, Polymer Journal, 16, 717 (1984), J. Randall et al. Reported by Asakura et al., “Macromol. Chem. Phys., 198, 1257 (1997) ". That is, the signals of methylene group and methine group are measured using ¹³ C nuclear magnetic resonance spectroscopy, and mesopentad fractions [mmmm], [mmrr] and [rmmr] are obtained. Here, when the value of the mesopentad fraction increases, it means that the stereoregularity of the polymer increases. If the mesopentad fraction is less than 20 mol%, stickiness may occur in a masterbatch composition using such an olefin polymer. On the other hand, when the mesopentad fraction exceeds 80 mol%, the master batch composition using the olefin polymer has an excessively high crystallization rate, making it difficult to increase the filling rate of the plastic additive.
The propylene-based polymer used in the present invention preferably has a stereoregularity index [mm] represented by a mesotriad fraction of 50 to 90 mol%, more preferably 50 to 80 mol%.
If the stereoregularity index is less than 50 mol%, stickiness may occur in the masterbatch composition containing such a propylene polymer, and if it exceeds 90 mol%, the masterbatch containing such a propylene polymer may be generated. There exists a possibility that the secondary processability of the polyolefin-type resin composition using a composition may fall.

(Ii) The olefin polymer used in the present invention is heated at 10 ° C./min up to 220 ° C. after holding 10 mg of a sample at −10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter. It is necessary that the melting point (Tm-D) is a crystalline resin having a melting point of 0 to 100 ° C. when the peak top observed on the highest temperature side of the peak observed from the melting endothermic curve obtained by the above is used. . The lower the melting point of the olefin polymer, the more preferable the use of the olefin polymer is because the heating temperature during the production of the masterbatch composition can be reduced, but it is not possible with an amorphous resin having no melting point. The resulting master batch composition is not preferable because stickiness is observed and handling properties as the master batch composition are lowered. About melting | fusing point, Preferably it is 20-90 degreeC, More preferably, it is 45-90 degreeC, More preferably, it is 60-90 degreeC, Most preferably, it is 60-80 degreeC.

(Iii) The olefin polymer used in the present invention has a weight average molecular weight (Mw) in the range of 10,000 to 1,000,000 as measured by gel permeation chromatography (GPC), preferably 10,000 to It is in the range of 150,000, particularly preferably in the range of 20,000 to 80,000. When Mw is less than 10,000, stickiness occurs in the masterbatch composition containing such an olefin polymer, and when it exceeds 1,000,000, polyolefin using the masterbatch composition containing such olefin polymer is used. Since the melt fluidity of the resin-based resin composition is lowered, the moldability becomes poor.
The olefin polymer used in the present invention has the above weight average molecular weight, and the Mw / Mn ratio Mw / Mn is 4 or less when the number average molecular weight in the measurement by the GPC method is Mn. Need to be satisfied. When the Mw / Mn exceeds 4, stickiness may occur in the master batch composition containing such an olefin polymer.

  In addition, said Mw / Mn is the weight average molecular weight (Mw) and number which were measured using GPC measuring apparatus [Column: TOSO, GMHHR-H (S) HT, detector: RI detector WATERS 150C for liquid chromatograms]. Calculated from the average molecular weight (Mn).

［式中、Ｍは周期律表第３〜１０族またはランタノイド系列の金属元素を示し、Ｅ¹及びＥ²はそれぞれ置換シクロペンタジエニル基，インデニル基，置換インデニル基，ヘテロシクロペンタジエニル基，置換ヘテロシクロペンタジエニル基，アミド基，ホスフィド基，炭化水素基及び珪素含有基の中から選ばれた配位子であって、Ａ¹及びＡ²を介して架橋構造を形成しており、又それらは互いに同一でも異なっていてもよく、Ｘはσ結合性の配位子を示し、Ｘが複数ある場合、複数のＸは同じでも異なっていてもよく、他のＸ，Ｅ¹，Ｅ²又はＹと架橋していてもよい。
Ｙはルイス塩基を示し、Ｙが複数ある場合、複数のＹは同じでも異なっていてもよく、他のＹ，Ｅ¹，Ｅ²又はＸと架橋していてもよく、Ａ¹及びＡ²は二つの配位子を結合する二価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、珪素含有基、ゲルマニウム含有基、スズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ₂−、−Ｓｅ−、−ＮＲ¹−、−ＰＲ¹−、−Ｐ（Ｏ）Ｒ¹−、−ＢＲ¹−又は−ＡｌＲ¹−を示し、Ｒ¹は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基又は炭素数１〜２０のハロゲン含有炭化水素基を示し、それらは互いに同一でも異なっていてもよい。
ｑは１〜５の整数で［（Ｍの原子価）−２］を示し、ｒは０〜３の整数を示す。］
で表される遷移金属化合物および（Ｂ）有機ホウ素化合物を含有する重合用触媒の存在下、炭素数２〜２０のα−オレフィン、好ましくはプロピレンもしくは１−ブテンを単独重合させる方法およびこれらα−オレフィンの２種以上を共重合させることにより得ることができる。 The olefin polymer used in the present invention is, for example, the method described in the third line of pages 8 to 9 of WO 03/091289 or the page of WO 03/070788, page 15, line 20. To page 17, line 3 and the like. (A) General formula (I)

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y.
Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other.
q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. ]
And (B) a method of homopolymerizing an α-olefin having 2 to 20 carbon atoms, preferably propylene or 1-butene, in the presence of a polymerization catalyst containing a transition metal compound and (B) an organic boron compound, and α- It can be obtained by copolymerizing two or more olefins.

C. Polyolefin resin for carrier The polyolefin resin for carrier used in the present invention is not particularly limited, but is more preferably the same as the polyolefin resin of the molding material used for the polyolefin resin composition. The melt flow rate (MFR, temperature: 230 ° C., load: 21.16 N) is selected from a polyolefin resin of 0.1 to 400 g / 10 minutes, preferably 5 to 250 g / 10 minutes. If the MFR is less than 0.1 g / 10 min, the compatibility of the molding material with the polyolefin-based resin is deteriorated, and the resulting molded product may be uneven in color or adversely affect various physical properties. is there. On the other hand, when the MFR exceeds 400 g / 10 min, it is difficult to produce a master batch composition, and various physical properties such as mechanical strength of the obtained molded article may be adversely affected. A commercially available product can be used as the polyolefin resin for the carrier.

D. Masterbatch composition The masterbatch composition of the present invention comprises 10 to 95% by mass of an additive for plastics, 1 to 50% by mass of an olefin polymer having specific physical properties, and 1 to 89% by mass of a polyolefin resin for a carrier. %, More preferably 30 to 90% by mass of an additive for plastics, 5 to 30% by mass of an olefin polymer having specific physical properties, and 5 of a polyolefin resin for a carrier. A master batch composition containing ~ 65% by mass, more preferably 35 to 85% by mass of an additive for plastics, 5 to 25% by mass of an olefin polymer having specific physical properties, and a polyolefin resin for a carrier It is a masterbatch composition contained in a proportion of 10 to 60% by mass. Among them, the olefin polymer is a propylene polymer satisfying (iv) a stereoregularity index [mm] of 50 to 90 mol% in addition to the specific physical property values of (i) to (iii). Is particularly preferred.
When the proportion of the additive for plastic is less than 10% by mass, it is more effective to directly mix with a polyolefin-based resin, for example, a polypropylene-based resin without substantially passing through a masterbatch. On the other hand, when the plastic additive is 95% by mass or more, the viscosity of the master batch composition becomes too large to be pelletized.
If the olefin polymer is 1% by mass or less, the additives aggregate and cause poor dispersion. If the olefin polymer is 50% by mass or more, the resulting master batch composition is sticky, and the master batch composition adheres to the pellets or the master batch composition. Stickiness occurs in a polyolefin molded body obtained by molding a polyolefin-based resin composition using the product.

Production method of masterbatch composition The method for mixing the additive for plastic, the olefin polymer having specific physical properties and the polyolefin resin for carrier is not particularly limited, and is a mixing roll, intensive mixer such as Banbury mixer, kneader, uniaxial Alternatively, a conventionally well-known method such as a twin screw extruder can be employed. Also, multistage mixing is possible, such as mixing the plastic additive and a part of the olefin polymer and then adding and mixing the remaining olefin polymer.

  The masterbatch composition of the present invention is optimally used at the time of molding a polypropylene resin composition for injection molding. However, an extrusion method other than the injection molding method, specifically, a T-die extrusion method, a calendar It can also be used in film / sheet molding by roll molding, hot compression molding, inflation molding, etc., and also in high-speed spinning molding.

Polyolefin-based resin composition The polyolefin-based resin of the molding material used in the polyolefin-based resin composition of the present invention is not particularly limited, and is an α-olefin homopolymer, an α-olefin copolymer, an α-olefin and a vinyl monomer. Copolymer, ethylene-unsaturated carboxylic acid ester copolymer, ethylene / carboxylic acid unsaturated ester copolymer, and the like. Among them, propylene homopolymer, propylene and ethylene or carbon number 4 to 20 Polypropylene resins such as copolymers with α-olefins are preferred. These polyolefin resins may be used alone or in combination of two or more.
As for the compounding quantity of the masterbatch composition mix | blended with this polyolefin resin, it is desirable that it is 0.1-10 mass parts with respect to 100 mass parts of this polyolefin resin. If the amount is less than 0.1 parts by mass, the effect of improving the polyolefin resin by the master batch composition cannot be obtained, and if the amount exceeds 10 parts by mass, there is no economic efficiency as the master batch composition.

  Unless it is contrary to the objective of this invention, thermoplastic resins other than polyolefin resin can be mix | blended with the polyolefin resin composition of this invention. Examples of the thermoplastic resin include polystyrene resins such as polystyrene, rubber-reinforced polystyrene (HIPS), isotactic polystyrene, and syndiotactic polystyrene; acrylonitrile-styrene resin (AS), acrylonitrile-butadiene-styrene resin (ABS). ) And other polyacrylonitrile resins; polymethacrylate resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene resins, polyphenylene ether resins, polyphenylene sulfide resins, polyphenylene sulfone resins, rosin resins, terpenes Resin, chroman and indene resin, petroleum resin, and the like. Of these, petroleum resin is preferable. In addition, these thermoplastic resins may be used independently and may be used in combination of 2 or more type. As for the compounding quantity of these thermoplastic resins, it is desirable that it is 0.1-100 mass parts with respect to 100 mass parts of polyolefin resin. If it is less than 0.1 part by mass, the improvement effect by the thermoplastic resin cannot be obtained. Moreover, when it exceeds 100 mass parts, the characteristics as a polyolefin-type resin composition will be lost.

In the polyolefin resin composition of the present invention, conventionally known foaming agents, crystal nucleating agents, anti-glare stabilizers, heat-resistant stabilizers, light stabilizers (hereinafter referred to as stabilizers), ultraviolet absorbers, light Stabilizer, heat stabilizer, antistatic agent, mold release agent, flame retardant, synthetic oil, wax, electrical property improver, anti-slip agent, anti-blocking agent, viscosity modifier, anti-coloring agent, anti-fogging agent, Additives such as lubricants, pigments, dyes, plasticizers, softeners, anti-aging agents, hydrochloric acid absorbers, chlorine scavengers, antioxidants, and anti-tacking agents can be added within the range that does not impair the purpose of the present invention. it can.
Examples of the stabilizer include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine stabilizers and metal salts of higher fatty acids, which are added to 100 parts by mass of polyolefin resin. And may be blended in an amount of 0.001 to 10 parts by mass.

As this phenolic antioxidant, 2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylene-bis- (4-methyl-6-t-butylphenol), tetrakis- [ Various known phenolic antioxidants such as methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane are used. Moreover, it is desirable to contain sulfur type antioxidant with said phenolic antioxidant. As the sulfur-based antioxidant, various known sulfur-based antioxidants such as dilauryl thiodipropionate and distearyl thiodipropionate are used. Furthermore, in order to further improve the effect of suppressing oxidative degradation, it is preferable to contain a phosphorus antioxidant together with the two types of antioxidants. Examples of the phosphorus antioxidant include various known ones such as triphenyl phosphite, trisnonylphenyl phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite. Phosphorous antioxidants are used.
If necessary, fillers such as conventionally known inorganic fillers and organic fillers can be further blended within a range that does not impair the object of the present invention.

  There is no restriction | limiting in particular about the shape of the inorganic filler and organic filler to be used, The thing of any shape, such as granular shape, plate shape, rod shape, fiber shape, whisker shape, can be used. Examples of inorganic fillers include silica, diatomaceous earth, barium ferrite, alumina, titanium oxide, magnesium oxide, beryllium oxide, oxides such as pumice and pumice balloons, water such as aluminum hydroxide, magnesium hydroxide, and basic magnesium carbonate. Oxides, carbonates such as calcium carbonate, magnesium carbonate, dolomite, dawsonite, sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass Balloons, glass beads, calcium silicate, montmorillonite, bentonite, kaolinite and other clay minerals and silicates and their organic compounds (organized clay), carbon black, graphite, carbon fibers, carbon hollow spheres and other charcoal S and, molybdenum sulfide, boron fiber, zinc borate, barium metaborate, calcium borate, sodium borate, magnesium oxysulfate, various metal fibers and the like. On the other hand, as organic fillers, for example, shell fibers such as fir shells, wood flour, cotton, jute, paper strips, cellophane pieces, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, polypropylene fibers, thermosetting Resin powder etc. can be mentioned.

  These inorganic fillers and organic fillers may be used alone or in combination of two or more. In the polyolefin resin composition for injection molding, among these, talc, mica, calcium carbonate, and glass fiber are preferable, and talc is particularly preferable. The size of the talc is such that the average particle size is 1 to 8 μm and the average aspect ratio is 4 or more from the viewpoint of physical properties such as rigidity, impact resistance, scratch resistance whitening, weld appearance, gloss unevenness, etc. Are preferred. In particular, those obtained by processing and pulverization are particularly preferred in terms of physical properties and rigidity. The compounding amount of the inorganic filler or organic filler is in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin. If the blending amount is less than 1 part by mass, the resulting molded article has insufficient rigidity, and if it exceeds 100 parts by mass, the resulting molded article has poor appearance such as weld appearance and uneven gloss, and has impact resistance and scratch resistance. Whitening property decreases. From the viewpoints of appearance, rigidity, impact resistance, scratch resistance and whitening resistance of the molded article, the preferred amount of the inorganic filler or organic filler is in the range of 3 to 60 parts by mass with respect to 100 parts by mass of the polyolefin resin. Especially, the range of 5 to 40 parts by mass is preferable.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

(1) Measurement of Intrinsic Viscosity Using a VMR-053 type automatic viscometer manufactured by Kouaisha Co., Ltd., it was measured at 135 ° C. in a tetralin solvent.
(2) Measurement of mesopentad fraction [mmmm]
The signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and the mesopentad fraction [mmmm] in the polyolefin molecule was determined.
The ¹³ C nuclear magnetic resonance spectrum was measured with the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds integration: In 10000 present invention, the stereoregularity index ([mm]) is used the JEOL Ltd. JNM-EX400 type device, ¹³ C-NMR spectrum of the conditions It is a value obtained by measuring in the same manner as above, and measuring the mesotriad ([mm]) fraction of the propylene chain.

(3) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) By GPC method, it measured with the following apparatus and conditions, and calculated | required weight average molecular weight Mw and number average molecular weight Mn.
GPC measurement device Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram, WATERS150C,
Measurement conditions Solvent; 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(4) Measurement of melting point (Tm-D) Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then 10 ° C. / The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature in minutes was defined as the melting point: Tm-D.

Production Example 1
(A) Catalyst preparation
(1) Production of 2-chlorodimethylsilylindene Under a nitrogen stream, 50 ml of THF (tetrahydrofuran) and 2.5 g (41 mmol) of magnesium were added to a 1 liter three-necked flask, and 1,2-dibromoethane was added to the flask. .1 ml was added and stirred for 30 minutes to activate the magnesium. After stirring, the solvent was extracted and 50 ml of THF was newly added. A solution of 5.0 g (25.6 mmol) of 2-bromoindene in THF (200 ml) was added dropwise thereto over 2 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., and a solution of 3.1 mL (25.6 mmol) of dichlorodimethylsilane in THF (100 mL) was added dropwise over 1 hour and stirred for 15 hours. Then, the solvent was distilled off. The residue was extracted with 200 ml of hexane, and then the solvent was distilled off to obtain 6.6 g (24.2 ml) of 2-chlorodimethylsilylindene (yield 94%).

(2) Production of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) Under a nitrogen stream, 400 ml of THF and 8 g of 2-chlorodimethylsilylindene were added to a 1-liter three-necked flask. Was added and cooled to -78 ° C. To this solution, 38.5 ml (38.5 mmol) of a THF solution (1.0 mol / liter) of LiN (SiMe ₃ ) ₂ was added dropwise. After stirring at room temperature for 15 hours, the solvent was distilled off and extracted with 300 ml of hexane. The solvent was distilled off to obtain 2.0 g (6.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) (yield 33.4%). ).
(3) [Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride]
In a 200 ml Schlenk bottle under a nitrogen stream, 2.5 g (7.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) obtained in (2) 100 ml of diethyl ether was added. After cooling to −78 ° C., 9.0 ml (14.8 mmol) of a hexane solution (1.6 mol / liter) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours. The solid obtained by distilling off the solvent was washed with 20 ml of hexane and dried under reduced pressure to quantitatively obtain a lithium salt as a white solid.
In a Schlenk bottle, lithium salt (6.97 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) was dissolved in 50 ml of THF, and iodomethyltrimethylsilane 2. 1 ml (14.2 mmol) was slowly added dropwise and stirred for 12 hours. Evaporate the solvent, add 50 ml of diethyl ether and wash with saturated ammonium chloride solution. After liquid separation, the organic phase is dried and the solvent is removed to remove 3.04 g (5.9) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene). Mmol) (yield 84%).
Next, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of diethyl ether. After cooling to −78 ° C., 7.4 ml (11.8 mmol) of a hexane solution (1.6 mol / liter) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to obtain 3.06 g of a lithium salt as a diethyl ether adduct.
The results of measurement by ¹ H-NMR (90 MHz, THF-d8) are: δ 0.04 (s, -SiMe ₃ , 18H), 0.48 (s, -Me ₂ Si-, 12H), 1.10. _{(t, -CH 3, 6H)} , 2.59 (s, -CH 2 -, 4H), 3.38 (q, -CH 2 -, 4H), 6.2-7.7 (m, Ar- H, 8H).
Under a nitrogen stream, 3.06 g of the lithium salt obtained above is suspended in 50 ml of toluene. The mixture was cooled to −78 ° C., and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to −78 ° C. in advance, in toluene (20 ml) was added dropwise. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The obtained residue was recrystallized from dichloromethane to obtain 0.9 g of yellow fine crystals of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride ( 1.33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are: δ 0.0 (s, —SiMe ₃ —, 18H), 1.0 ₂ , 1.12 (s, —Me ₂ Si—, 12H ), 2.51 (dd, —CH ₂ —, 4H), 7.1 to 7.6 (m, Ar—H, 8H) (b) Polymerization In a 1 liter autoclave heated to dryness, 200 ml of heptane, 1 -200 ml of butene, 0.2 mmol of triisobutylaluminum, 2 μmol of dimethylanilinium borate were added, and 0.05 Pa of hydrogen was further introduced. After the temperature was raised to 80 ° C. with stirring, 0.4 micromol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3trimethylsilylmethylindenyl) zirconium dichloride was added and polymerized for 60 minutes. . After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 90 g of a 1-butene polymer as an olefin polymer. The properties of the obtained 1-butene polymer are shown in Table 1.

Production Example 2
Production of low molecular weight propylene-based polymer A stainless steel reactor with a stirrer and an internal volume of 0.25 m ³ , n-heptane at 20 liter / h, triisobutylaluminum at 16 mmol / h, methylaluminoxane at 15 mmol / h, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium chloride obtained according to Production Example 1 was continuously supplied at 15 μmol / h. Propylene and hydrogen were continuously supplied at a polymerization temperature of 60 ° C. so that the gas phase hydrogen concentration was 54 mol% and the total pressure in the reactor was maintained at 0.75 MPa · G. The polymerization solution was continuously extracted, and 500 ppm of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added to the resulting polymerization solution, and the solvent was removed at a jacket temperature of 200 ° C. to obtain a low molecular weight propylene polymer. Obtained. The stereoregularity index [mm] was 58 mol%.

Example 1
Laboplastmill biaxially prepared 250 g of polypropylene resin (Y6005GM Idemitsu Kosan Co., Ltd.), 200 g of carbon black (Black Pearls800 Cabot) and 50 g of the olefin polymer (low molecular weight propylene polymer) obtained in Production Example 2 as a dispersant. In an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a master batch composition was granulated by melting and kneading while degassing with a vent under the conditions of 200 ° C. and screw rotation speed of 280 rpm. The discharge amount measured at the die outlet is shown in Table 2.
The pigment dispersion performance of the obtained pigment master batch pellets was measured by the following procedure.
For 100 parts by mass of polypropylene (J-950HP Idemitsu Kosan Co., Ltd.), 2 parts by mass of the prepared pigment master batch pellets were dry blended to prepare a polypropylene resin composition, and the composition was used under the following conditions. An injection-molded body was molded.
Injection molding machine: Toshiba Machine Co., Ltd. IS200CN (clamping force 200t)
Mold: 420 × 100 × 3 mm flat resin temperature: 220 ° C., mold temperature: 45 ° C., filling time: 5 seconds back pressure: 588 kPa (gauge pressure), holding pressure: 5 seconds filling pressure × 0.7
Holding pressure time: 5 seconds, cooling time: 25 seconds.
A 3 cm x 2 cm range is arbitrarily selected for each sample on the surface of the molded injection molded body, and the number of pigment lumps existing within the range is determined using PROFILE PROJECTOR V-24B manufactured by Nikon Corporation. Measured.
Next, the average number of lumps of the three pigments measured was calculated and converted into the number per unit area, and this was shown as “average number of lumps (pieces / cm ² )”.

Example 2
The same procedure as in Example 1 was performed except that carbon black was changed to Vulcan 9A32 (Cabot Corporation).

Example 3
The same procedure as in Example 1 was carried out except that the olefin polymer in Example 1 was changed to the 1-butene polymer obtained in Production Example 1.

Comparative Example 1
250 g of polypropylene resin (Y6005GM Idemitsu Kosan Co., Ltd.) and 250 g of carbon black (Black Pearls800 Cabot) are used at a lab plast mill twin screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 200 ° C. and screw rotation speed of 280 rpm. The pigment master batch composition was granulated by melting and kneading while venting. The discharge amount measured at the die outlet is shown in Table 2. The pigment dispersion performance of the obtained pigment master batch pellets was measured according to Example 1.

Comparative Example 2
250 g of polypropylene resin (Y6005GM Idemitsu Kosan Co., Ltd.), Viscol P660 (Tm-D: olefin copolymer of about 130 ° C., manufactured by Sanyo Chemical Industries, Ltd.) 50 g as an olefin polymer, carbon black (Black Pearls 800 Cabot) 200g is melted and kneaded with a lab plast mill twin screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the conditions of 200 ° C. and screw rotation speed of 280 rpm while venting, to obtain a pigment master batch composition. Granulated. The discharge amount measured at the die outlet is shown in Table 2. The pigment dispersion performance of the obtained pigment master batch pellets was measured according to Example 1.

Example 4
90 g of the olefin polymer of Production Example 2, 90 g of LDPE (Asahi Kasei Co., Ltd. L1885) and 120 g of a foaming agent (Selbon SK-C Eiwa Kasei Co., Ltd.) were added at a cylinder temperature of 100 with a 20 mmφ single-screw extruder (Tsukada Kikai Seisakusho). The mixture was kneaded and granulated under the conditions of 1 ° C. and a screw rotation number of 1100 rpm. 0.5 g of the obtained pellet sample was set in a heating furnace of a Karl Fischer apparatus under air, sealed, and heated at 150 ° C. The gas generated at this time was collected in a 25 ml graduated cylinder sealed with water and collected for 16 minutes in a state where the water surfaces were combined. The same measurement was performed without a sample to obtain a blank. The amount of generated gas was 18.7 ml / g by subtracting the blank from the collected gas amount, and it was confirmed that the foaming agent was contained in the pellets.

Comparative Example 3
In Example 4, the sample was made of 240 g LDPE (Asahi Kasei Co., Ltd. L1885) and 60 g blowing agent (Celbon SK-C Eiwa Kasei) without using the olefin polymer of Production Example 2, and a 20 mmφ single screw extruder (Tsukada). As a result of kneading at a cylinder temperature of 180 ° C. and trying granulation, the foaming in the extruder was intense and kneading could not be carried out, so that a sample could not be obtained.

Comparative Example 4
240 g of the olefin polymer of Production Example 2 and 60 g of a foaming agent (Selbon SK-C Eiwa Kasei) were kneaded with a 20 mmφ single-screw extruder (Tsukada Kikai Seisakusho) under the conditions of a cylinder temperature of 100 ° C. and a screw rotation speed of 1100 rpm As a result of attempts at granulation, strand breakage occurred and stable granulation was difficult.
0.5 g of the obtained pellet sample was set in a heating furnace of a Karl Fischer apparatus under air, sealed, and heated at 150 ° C. The gas generated at this time was collected in a 25 ml graduated cylinder sealed with water and collected for 16 minutes in a state where the water surfaces were combined. The same measurement was performed without a sample to obtain a blank. The amount of generated gas was 10.5 ml / g by subtracting a blank from the collected gas amount.

Claims (8)

Master batch containing 35 to 85% by mass of plastic additive, 5 to 25% by mass of olefin polymer satisfying the following (i) to (iii), and 10 to 60% by mass of polyolefin resin for carrier Composition.
(I) Mesopentad fraction [mmmm] is 20 to 80 mol%,
(ii) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. A melting point (Tm-D) defined as the observed peak top of 0-100 ° C.,
(Iii) When the weight average molecular weight (Mw) in the measurement by gel permeation chromatography (GPC) method is in the range of 10,000 to 80,000 and the number average molecular weight in the measurement by GPC method is Mn The Mw / Mn ratio Mw / Mn is 4 or less. The masterbatch composition according to claim 1, wherein the olefin polymer is a propylene polymer that further satisfies the following (iv).
(Iv) Stereoregularity index [mm] is 50 to 90 mol%.   A polyolefin-based resin composition obtained by blending the masterbatch composition according to claim 1 or 2 with a polyolefin-based resin.   The production of a polyolefin resin composition according to claim 3, wherein 0.1 to 10 parts by mass of the master batch composition according to claim 1 or 2 is blended with 100 parts by mass of the polyolefin resin. Method.   The polyolefin resin composition according to claim 3, wherein the polyolefin resin is a polypropylene resin.   The method for producing a polyolefin resin composition according to claim 4, wherein the polyolefin resin is a polypropylene resin.   The manufacturing method of the polyolefin molded object by injection-molding the polyolefin resin composition of Claim 3 or 5.   An automobile injection-molded product obtained by injection molding using the polyolefin-based resin composition according to claim 3 or 5.